CN115312675A - Diffusion-limited electroactive barrier for photovoltaic modules - Google Patents

Diffusion-limited electroactive barrier for photovoltaic modules Download PDF

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CN115312675A
CN115312675A CN202210960794.0A CN202210960794A CN115312675A CN 115312675 A CN115312675 A CN 115312675A CN 202210960794 A CN202210960794 A CN 202210960794A CN 115312675 A CN115312675 A CN 115312675A
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layer
electron
hole
transport layer
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马尔钦·拉塔伊恰克
帕特里克·巴尔科夫斯基
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Inuru GmbH
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/731—Liquid crystalline materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to a diffusion-limiting electroactive barrier for photovoltaic components having a cathode, an anode and a layer system between the cathode and the anode, which comprises an electroactive layer, in particular a charge carrier injection and transport layer, and which comprises a photoactive layer, the charge carrier injection and transport layer itself being a diffusion barrier for water or oxygen.

Description

Diffusion-limited electroactive barrier for photovoltaic modules
The present application is a divisional application of the invention application having an application number of "201780070887.3" entitled "diffusion-limited electroactive barrier layer for photovoltaic module".
Technical Field
The invention relates to an optoelectronic component having a cathode, an anode and a layer system located between the cathode and the anode, which comprises an electroactive layer, in particular a charge carrier injection and transport layer, and which comprises an photoactive layer, the charge carrier injection and transport layer itself being a diffusion barrier for water or oxygen.
Background
The invention relates to the field of optoelectronic components. Photovoltaic modules, for example, organic-based or hybrid modules made of organic and inorganic layers, are widely used in the art.
Organic Light Emitting Diodes (OLEDs) generally consist of a sandwich structure, in which a plurality of layers of organic semiconductor material are present between two electrodes. In particular, OLEDs comprise one or more Emissive Layers (EL) in which electromagnetic radiation, preferably in the visible range, is generated by recombination of electrons and electron holes. The electrons and electron holes are each provided by the cathode or anode, wherein preferably a so-called injection layer facilitates this process by lowering the injection barrier. Therefore, OLEDs generally have an electron injection layer or a hole injection layer. In addition, OLEDs typically have an Electron Transport Layer (ETL) and a Hole Transport Layer (HTL), which support the diffusion direction of electrons and holes to the emissive layer. In an OLED, these layers are formed of organic materials; in a hybrid photovoltaic module, the layers may be made partly of organic material and partly of inorganic material.
Compared to conventional inorganic LEDs, OLEDs and hybrid LEDs are characterized by a thin and flexible layer structure. For this reason, OLEDs and hybrid LEDs can have more diverse uses than traditional inorganic LEDs. Due to their flexibility, OLEDs can be excellently used for e.g. screens, electronic paper or indoor lighting.
The advantageous properties of optoelectronic components (OLEDs or hybrid LEDs) comprising organic semiconductor materials for the generation of light can also be transferred to the generation of electricity. Therefore, organic or hybrid solar cells are also characterized by a thin-layer structure, which significantly increases the possible uses compared to conventional inorganic solar cells. The structure of an organic solar cell or hybrid solar cell has similarities to an OLED or hybrid LED.
However, instead of an emissive layer, one or more absorber layers are present as photoactive layers. Due to the incident electromagnetic radiation, electron-hole pairs are generated in the absorption layer as free charge carriers. The other layers include an electron transport layer and a hole transport layer, and an electron extraction layer and a hole extraction layer. They consist of organic materials or, in the case of mixtures, of organic and inorganic materials, the electrochemical potentials of which move as donor and acceptor layers, so that they generate an internal field in the solar cell which dissipates free charge carriers to the electrodes. As a result of the incidence of electromagnetic radiation, electrons are provided at the cathode and electron holes are provided at the anode to generate a voltage or current.
Due to the thin-film structure, organic solar cells can be produced inexpensively and can be applied to buildings over a large area as film coatings.
Other possible applications of optoelectronic components made of organic or inorganic-organic layers are, for example, photodetectors. They also utilize the photoelectric effect, where electron-hole pairs are generated in the photoactive layer. They do not generate electricity as in solar cells, but are used to detect light, for example for cameras.
The thin-layer structure of the photoelectric component can be used more flexibly in daily life, and has the characteristic of high cost-effective manufacturing selection compared with the traditional LED, solar cell or photoelectric detector.
In contrast, however, the disadvantage of the thin-film structure is that the lifetime of these optoelectronic components is generally short compared to conventional structures. In particular, the destruction on the electronically active layer by water vapor or oxygen leads to signs of wear and a reduced efficiency coefficient. Unlike conventional structures, the thin layer structure is not coated with glass or other water or oxygen resistant materials. Chemical hydrocarbon compounds of organic or mixed composition are also more susceptible to chemical or physical degradation processes.
For this purpose, various techniques for encapsulating photovoltaic modules are used in the known prior art to prevent the permeation of harmful water vapor or oxidation by oxygen.
For example, in WO2011/018356 a method is described in which a pressure sensitive adhesive is applied around an electronic device as a barrier layer. The barrier layer works like a capsule to prevent permeation of permeants and extend the life of the OLED.
In addition, WO2014/048971 discloses an encapsulant for optoelectronic components made of a mixture of inorganic substances, which encapsulant is also applied as an adhesive layer. The encapsulant serves to achieve a hermetic seal of the electrically active region of the OLED or solar cell, in particular against water vapor or oxygen.
In the known prior art, photovoltaic modules are initially manufactured under a protective atmosphere (usually made of nitrogen). For this purpose, solvent-based processes and vacuum thermal vapor deposition are used. After the actual organic or hybrid photovoltaic module has been manufactured, it is encapsulated with a special film or glass to protect it in particular from oxygen and water. In addition, it is also possible to place a thin layer of absorbent material (so-called getter material) generally between the assembly and the barrier capsule (made, for example, of glass or a special plastic film). This serves to bind water or oxygen already present. As a barrier layer for encapsulation, glass is characterized by low permeability to water. However, glass is not flexible. Therefore, for applications requiring thin electronic devices that are flexible, for example, for displays, sensors, transistors, solar cells, etc., encapsulation is often performed with plastic films having special coatings that form barrier layers. Plastic films (e.g., PET, PEN, etc.) do not generally provide sufficient barrier effect by themselves. The barrier properties of these films are therefore based on special coatings and the following phenomena: water or oxygen molecules are generally not able to penetrate the inorganic barrier layer. However, perfect thin inorganic barrier layers have never been produced, and in most cases small nanometer-sized defects appear, which diffuse or migrate through the separated molecules. The second layer is diffusion-limited and placed between the respective inorganic barrier layers for increasing the (diffusion) path length of the respective water or oxygen molecules until they again reach the defects in the second barrier layer. Thus, barrier films typically comprise a structure having alternating barrier layers or diffusion barrier layers and diffusion limiting layers, which layers as a whole result in acceptable barrier properties and thus prevent the penetration of water vapour or oxygen. In the prior art, permeation is usually expressed by Vapor Transmission Rate (VTR), or, particularly for water, by Water Vapor Transmission Rate (WVTR)And (4) showing. The WVTR and VTR values for barrier films or barrier substrates from the prior art are typically in the range of 1 to 10 -6 Gram of water/(24 hours cm) 2 Barrier surface area) or cm 3 Steam/(24 hours cm) 2 Barrier surface area). Commercial barrier films or barrier substrates used for encapsulation have a thickness of between 25 and 100 micrometers (μm). For flexible applications, barrier films are typically applied in a self-adhesive manner to both sides of the photovoltaic assembly. In the prior art, the individual layers of the barrier film and the entire barrier film itself do not have the electrical characteristics for conducting charge carriers, but merely serve to protect the component from degradation processes due to water or oxygen.
A disadvantage of the known method and the use of a barrier film is in particular the large layer thickness. The total thickness of the barrier film is at least 50 micrometers due to the necessary carrier substrate (i.e. typically a plastic film) and the functional barrier layer (i.e. the described inorganic barrier layer (diffusion barrier layer) and diffusion limiting layer). The optoelectronic component itself to be encapsulated is typically only about 50 microns thick. By encapsulating on both sides, the encapsulation thus results in a thickness of the component of 3 times the total minimum thickness of 150 μm compared to the possible 50 μm. As a result, the rigidity of the component to be packaged increases and its flexibility decreases. As a result, possible applications, such as applications related to electronic paper, are significantly limited. In addition, in the packaging of the components, problems may arise with the barrier film at the edges of the components to be bonded. At these points, there is an increased mechanical load due to the flexibility and the barrier film may fall off despite the adhesive layer and the adhesive, which results in reduced protection and a shortened service life. In addition, during encapsulation, i.e. in particular during adhesion of the barrier film, air pockets often occur between the barrier film and the component. This increases the failure rate of the manufactured optoelectronic component and thus increases the cost. The manufacturing cost is further increased due to the relatively high cost of the barrier film and the need for additional processing steps that increase the likelihood of defects occurring. In addition, since the transmittance of the barrier film is lowered and the dispersion is higher, the optical characteristics may be limited.
Layered OLEDs having individual functional elements, for example electrodes, with barrier-like properties are also known from the prior art. However, the associated individual injection or extraction and transport layers of no known OLED also have barrier-like properties for water and oxygen. Furthermore, it is not known to use printing methods for the construction of such OLEDs.
Object of the Invention
It is therefore an object of the present invention to provide an optoelectronic component which ameliorates the above-mentioned disadvantages of the prior art. In particular, an optoelectronic component should be provided which differs from the prior art in cost-effectiveness of manufacture, high durability and high flexibility due to the small thickness.
Disclosure of Invention
The object according to the invention is achieved by an optoelectronic component and a method for manufacturing the component according to the independent claims. The independent claims represent preferred embodiments of the invention.
In a preferred embodiment, the invention relates to a photovoltaic module having a cathode and an anode and a layer system between the cathode and the anode, comprising at least one electron injection layer or electron extraction layer adjacent to the cathode, at least one electron transport layer, at least one photoactive layer, at least one hole transport layer, at least one hole injection layer or hole extraction layer adjacent to the anode, characterized in that the at least one electron injection layer or electron extraction layer and the at least one hole injection layer or hole extraction layer have diffusion-limiting properties with respect to water and/or oxygen and the at least one electron transport layer and the at least one hole transport layer correspond to diffusion barriers with respect to water and/or oxygen.
The photovoltaic module according to the invention is preferably characterized in that it comprises an electrode (i.e. an anode or a cathode), a photoactive layer and an electroactive layer (i.e. in particular a charge carrier injection layer or a charge carrier extraction layer and a charge carrier transport layer). The function of the photovoltaic module is preferably characterized by a photoactive layer, which is used in particular for generating light or electricity. For the purposes of the present invention, an electroactive layer preferably means a layer which ensures the electrical functionality of the component and is arranged between the photoactive layer and the electrode. For the purposes of the present invention, the charge carrier injection layer or the charge carrier extraction layer and the charge carrier transport layer are electroactive layers. Furthermore, for the purposes of the present invention, charge carriers preferably mean electrons or electron holes. The terms hole and electron-hole are preferably used synonymously in the following. Those skilled in the art know how to arrange an electroactive layer in accordance with a photoactive layer to achieve the desired functionality of an optoelectronic assembly.
Basically, the invention preferably relates to two sets of optoelectronic components. In the first group, the photoactive layer is preferably an emissive layer for generating light. In this case, the optoelectronic component is preferably used as an organic or hybrid Light Emitting Diode (LED). In the second group, the photoactive layer is preferably an absorber layer in which free charge carriers are generated by absorption of electromagnetic radiation. Thus, in the second group, the photovoltaic component is preferably an organic or hybrid solar cell or photodetector.
As described above, the electrical layer is selected to ensure the functionality of the photoactive layer of the assembly.
In a preferred embodiment, the invention relates to an optoelectronic component for generating light, for example as a light-emitting diode. In this preferred embodiment, the photovoltaic module has a cathode and an anode and a layer system between the cathode and the anode, which comprises at least one electron injection layer adjacent to the cathode, at least one electron transport layer, at least one photoactive layer as emission layer, at least one hole transport layer, at least one hole injection layer adjacent to the anode, and is characterized in that the at least one electron injection layer and the at least one hole injection layer are diffusion-limited with respect to water and/or oxygen and the at least one electron transport layer and the at least one hole transport layer correspond to diffusion barriers with respect to water and/or oxygen.
In this preferred embodiment, the cathode serves as an electron donor. Preferably, the cathode has a low sheet resistance in order to promote the most uniform possible injection of electrons across the surface of the OLED.
On the other hand, the electron injection layer performs a function of matching the work function of the cathode with a subsequent layer (i.e., an electron transport layer). The work function preferably corresponds to the energy which has to be consumed in order to remove at least electrons from uncharged solids. By matching the work function of the cathode to the electron transport layer, the voltage required to inject electrons from the cathode into the electron transport layer is reduced.
The electron transport layer provides for the directed electron transport between the cathode and the photoactive layer (i.e., preferred embodiments of the emissive layer). Therefore, the electron transport layer should preferably have sufficient electron mobility or mobility (preferably 10) -6 To 100cm 2 V sec). In addition, the charge transport level of the electron transport layer, i.e. the charge band or LUMO (lowest unoccupied molecular orbital), should preferably be between the energy level of the emissive material and the work function of the cathode, i.e. no additional energy is required to transport electrons before recombination with holes after performing the work function.
The emissive layer preferably consists of a semiconducting organic polymer or molecule, which under electrical stimulation generates light in the visible range, i.e. preferably in the wavelength range of 400-700 nm. In the emission layer, electrons of the cathode preferably recombine with holes of the anode to form excitons. Preferably, the amount of singlet excitons dominates so that light is efficiently generated.
The hole transport layer is the counterpart of the electron transport layer for transporting (electron) holes from the anode to the emissive layer. Thus, preferably, the hole transport layer should have sufficient electron-hole mobility or mobility, preferably 10 -6 To 100cm 2 V sec. In addition, the electron hole transport energy level (i.e. the charge band or HOMO (highest occupied molecular orbital)) of the hole transport layer should preferably be between the energy level of the emissive material and the work function of the anode.
The hole injection layer, like its counterpart (electron injection layer) on the cathode side, is preferably composed of a strong dielectric polymer, and is preferably an insulator. Preferably, the hole injection layer serves to balance the energy levels of the anode and subsequent layers (hole transport layer) to ensure efficient injection of electron holes.
The anode is preferably an electron hole donor and therefore preferably has a significantly higher work function than the cathode. In addition, the anode preferably has high hole surface conductivity. In addition, preferably, the anode material may be transparent to preferably allow light emission through the anode.
In this preferred embodiment, the photoactive layer is an emissive layer and the electroactive layers are at least one electron injection layer, at least one electron transport layer, at least one hole transport layer, and at least one hole injection layer.
For preferred embodiments in which the assembly will generate electricity rather than light, one skilled in the art will be able to adjust the electroactive and photoactive layers as follows.
The photoactive layer used is preferably an absorption layer which is capable of converting the energy of incident electromagnetic radiation into the generation of free charge carriers by photon absorption. The electroactive layer preferably ensures that an internal electric field is generated within the optoelectronic component, which internal electric field removes charge carriers from the respective electrodes. Electrons are extracted at the cathode and holes are extracted at the anode. The potential difference thus provided is used to generate a voltage or to generate a current under load.
In this preferred embodiment of the photovoltaic module, the layer structure is preferably as follows.
The photovoltaic module has a cathode and an anode and a layer system between the cathode and the anode, which comprises at least one electron extraction layer adjacent to the cathode, at least one electron transport layer, at least one photoactive layer as absorption layer, at least one hole transport layer, at least one hole extraction layer adjacent to the anode and is characterized in that the at least one electron extraction layer and the at least one hole extraction layer have diffusion-limiting properties with respect to water and/or oxygen and the at least one electron injection layer and the at least one hole transport layer correspond to diffusion barriers with respect to water and/or oxygen.
The electroactive layer is in turn designed to ensure the function of the absorption layer and efficient extraction of charge carriers. In this preferred embodiment, the photoactive layer is an absorbing layer and the electroactive layers are at least one electron extraction layer, at least one electron transport layer, at least one hole extraction layer, and at least one hole transport layer.
According to the invention, it has been found that, in order to prolong the service life of the optoelectronic component, the photoactive layer should be protected in particular against the damaging effects of water or water vapor and oxygen. Although the prior art mostly encapsulates the entire assembly, according to the invention an electroactive layer is used to achieve a barrier function against water or oxygen.
In the light generating assembly, the at least one electron injection layer and the at least one hole injection layer have diffusion limitations for water and/or oxygen. The at least one electron transport layer and the at least one hole transport layer form a diffusion barrier to water and/or oxygen.
In contrast, in the case of an electricity generating component, the electron extraction layer and the hole extraction layer have diffusion limitations for water and/or oxygen. The at least one electron transport layer and the at least one hole transport layer also form a diffusion barrier to water and/or oxygen.
Due to the dual function of the electroactive layer both as a permeation barrier for water and oxygen and supporting the directed current of charge carriers, the assembly can be constructed significantly more compactly. Although the use of barrier films is required in the prior art, thereby generally tripling the overall thickness of the assembly; this is advantageously eliminated in the layer structure according to the invention. The optoelectronic component is therefore significantly more flexible and can be realized flexibly. There are no additional manufacturing steps for the application of the barrier film, thereby significantly simplifying the manufacturing process and reducing the cost. By using the electroactive layer as a diffusion limiting layer or diffusion barrier, these components can be manufactured more reliably and cost effectively than in the prior art. The technical advances achieved by the invention are further shown in more powerful components which have a higher intensity and better optical properties (lower dispersion, monochromatic light) with the same electrical power consumption or generate more electrical power with the same intensity of solar radiation. Here, the method of the inventors' innovative research and system is rewarded by using an electroactive layer as a barrier to oxygen and water, and a new approach is adopted.
Surprisingly, an electroactive layer can be provided which provides both a blocking function and an electrical function for directing charge current. Since each individual layer having an electrical function also has a barrier function against oxygen and water, a surprisingly effective barrier against them can be achieved. Thus, the blocking function of each individual layer significantly increases the lifetime of the photovoltaic module. The effect that can be achieved by the interaction of the different barrier layers is significantly greater than that of a single barrier layer. The more layers with barrier properties are arranged on top of each other, the greater the effect of their nonlinear interaction, wherein the barrier effect of the combination of several barrier layers is preferably higher than that achieved by the sum of the barrier effects of the individual layers. This shows a synergistic effect. In this respect, both barrier properties and barrier properties refer to diffusion limiting properties and diffusion barrier properties.
There is also no problem at the edges of the assembly as opposed to the use of a barrier film. In contrast to the macrostructure of the barrier film, macroscopical gaseous inclusions such as occur in the barrier film can be effectively prevented due to the microstructure of the electroactive layer.
As described below, it is surprising that, in particular by selecting suitable materials and layer thicknesses, the barrier properties and the desired electrical properties of the electroactive layer can be achieved.
For the purposes of the present invention, the property of "diffusion-limiting with respect to water and/or oxygen" preferably means that the corresponding injection layer or extraction layer significantly reduces the diffusion of water and/or oxygen molecules. Thus, it is preferred that the path length of water and oxygen molecules in the layer can be increased by the diffusion limiting layer so that the molecules do not reach the photoactive layer.
In a preferred embodiment, the diffusion limiting layer has a thickness of less than 1 g/(m) 2 * d) And a Water Vapor Transmission Rate (WVTR) of less than 1cm 3 /(m 2 * d) Oxygen Transmission Rate (OTR).
For the purposes of the present invention, the property "diffusion barrier layer" is preferably understood to mean that the corresponding electron-transport layer or hole-transport layer prevents or significantly reduces the penetration of water and/or oxygen molecules. In a preferred embodiment, the electron-transport layer or the hole-transport layer as a diffusion barrier has less than 0.1 g/(m) 2 * d) And a Water Vapor Transmission Rate (WVTR) of less than 0.1cm 3 /(m 2 * d) Oxygen Transmission Rate (OTR).
It is particularly preferred, however, that the barrier properties of the electroactive layer together with the electrode meet the conditions that ensure effective protection of the photoactive layer from water or oxygen permeation.
In a further preferred embodiment, the photovoltaic module is characterized in that the layer combination of the cathode, the at least one electron-injecting or electron-extracting layer and the at least one electron-transporting layer has a value of less than 0.01 g/(m) 2 * d) And a Water Vapor Transmission Rate (WVTR) of less than 0.01cm 3 /(m 2 * d) And/or the layer combination of the anode, the at least one hole injection layer or hole extraction layer and the at least one electron transport layer has an Oxygen Transmission Rate (OTR) of less than 0.01 g/(m) 2 * d) And a Water Vapor Transmission Rate (WVTR) of less than 0.01cm 3 /(m 2 * d) Oxygen Transmission Rate (OTR). Depending on their composition and thickness, the skilled person can routinely adjust the layers such that the mentioned transmission rates can be achieved.
It has been realized that preferably the respective diffusion limiting layer or diffusion barrier layer does not have to fulfil the quantitative barrier properties, but particularly preferably the layer combination of the electrode and the electroactive layer to the photoactive layer has to fulfil the quantitative barrier properties. Thus, it may be preferred that the combination of the electrode and the injection layer or the extraction layer and the transport layer preferably has less than 0.01 g/(m) 2 * d) Or less than 0.01cm 3 /(m 2 * d) WVTR or OTR. However, the assembly may also preferably comprise a plurality of preferably alternating injection layers or extraction layers and transport layers, wherein the layer combination (e.g. cathode and all electron injection layers and electron transport layers) has less than 0.01 g/(m) 2 * d) Or less than 0.01cm 3 /(m 2 * d) WVTR or OTR. The same correspondingly applies to the other electroactive layers. That is, the layer combination of the anode and all of the hole injection layer and the hole transport layer preferably has a value of less than 0.01 g/(m) 2 * d) Or less than 0.01cm 3 /(m 2 * d) WVTR or OTR. For embodiments of the power generation assembly such as a solar cell or photodetector, the injection layer is replaced by an extraction layer in a layer combination.
Surprisingly, the WVTR or OTR value of the layer combination is less than 0.01 g/(m) 2 * d) Or less than 0.01cm 3 /(m 2 * d) Resulting in a particularly effective protection of the photoactive layer.Thus, for the preferred embodiment, the lifetime of the preferred solar cell or LED is significantly increased.
This embodiment with the above values represents a particularly maintenance-free assembly due to the strong synergistic barrier properties resulting from the combination of the individual layers.
The light emitting construction of the assembly plays an important role for use in printed products. The embodiments presented herein have proven to be particularly error-free in paper printing.
It may also be preferred that, in a further preferred embodiment, the photovoltaic component is characterized in that the layer combination of the cathode, the at least one electron injection or extraction layer and the at least one electron transport layer has a value of less than 0.1 g/(m) 2 * d) And a Water Vapor Transmission Rate (WVTR) of less than 0.1cm 3 /(m 2 * d) And/or the layer combination of the anode, the at least one hole injection layer or hole extraction layer and the at least one electron transport layer has an Oxygen Transmission Rate (OTR) of less than 0.1 g/(m 2 * d) And a Water Vapor Transmission Rate (WVTR) of less than 0.1cm 3 /(m 2 * d) Oxygen Transmission Rate (OTR). Thus, the combination of the electrode and the injection layer or the extraction layer and the transport layer may preferably have a value of less than 0.1 g/(m) 2 * d) Or less than 0.1cm 3 /(m 2 * d) WVTR or OTR. However, the assembly may also preferably comprise a plurality of preferably alternating injection or extraction and transport layers, wherein the layer combination (e.g. cathode and all electron injection and transport layers) has less than 0.1 g/(m) of 2 * d) Or less than 0.1cm 3 /(m 2 * d) WVTR or OTR. The same correspondingly applies to the other electroactive layers. That is, the layer combination of the anode and all of the hole-injecting layer and the hole-transporting layer may also preferably have a value of less than 0.1 g/(m) 2 * d) Or less than 0.1cm 3 /(m 2 * d) WVTR or OTR. For embodiments of power generation components such as solar cells or photodetectors, the injection layer will be replaced by an extraction layer in a layer combination.
By recognizing that it may be sufficient for certain embodiments to achieve the stated values for the combination of layers, particularly thin layers may be used to achieve the desired functionality.
Surprisingly, the layerThe combined WVTR or OTR value is less than 0.1 g/(m) 2 * d) Or less than 0.1cm 3 /(m 2 * d) Resulting in a component having particularly reliable electrical properties which can be determined in advance, while the component is sufficiently protected from oxygen and water. Furthermore, particularly thin layers can be used, with good protective properties, so that the service life of the component is long. Thus, a surprisingly durable and flexible assembly is achieved.
In this way, a lighting assembly having particularly advantageous aesthetic properties (optical brightness) can also be achieved. Therefore, the light emitting assembly having the above characteristics can also be used for very thin paper, such as paper for daily newspapers, to achieve an optical effect (e.g., a flashlight for vehicle advertising).
For the purposes of the present invention, water Vapor Transmission Rate (WVTR) preferably represents a measure of the permeability of water vapor or water molecules through a single layer or through a combination of layers. To determine the WVTR value, the mass of water molecules diffusing through the region of the layer within 24 hours is preferably determined. In this case, the preferred unit is g/(m) 2 * d) WVTR, where SI units g represents g, d represents day (i.e., 24 hours), m 2 Representing the square meter of the area of the layer or combination of layers.
In the same way, for the purposes of the present invention, the Oxygen Transmission Rate (OTR) preferably represents a measure of the permeability of oxygen molecules through a monolayer or through a combination of layers. To determine the OTR value, the gas volume of the oxygen molecules diffusing through the region of the layer within 24 hours is preferably determined. In this case, the preferred unit is in cm 3 /(m 2 * d) OTR of formula (I), wherein SI is in cm 3 Representing cubic centimeters, d represents days (i.e., 24 hours), m 2 Represents the square meter, i.e. the area of a layer or a combination of layers.
The skilled person knows how to determine the OTR and WVTR of the thin film by experimentation and can therefore select the layer according to these properties.
For example, the American Society for Testing and Materials (ASTM) discloses experimental tests for determining the OTR and WVTR of thin layers of photovoltaic modules under ASTM D1653-13 entitled standard test method for water vapor transmission rates of organic coating films. A document describing the trial was downloaded on 12.9.2016 from https:// www.astm.org/Standards/D1653. Htm.
In a preferred embodiment of the invention, the optoelectronic component is characterized in that the at least one electron transport layer and the at least one hole transport layer have a length of less than 0.1cm 3 /(m 2 * d) And an Oxygen Transmission Rate (OTR) of less than 0.1 g/(m) 2 * d) Water Vapor Transmission Rate (WVTR). Advantageously, these parameter values of the individual transport layers result in an effective avoidance of the penetration of water or oxygen molecules. The inventors have found that the electron transport layer and the hole transport layer are particularly important in this respect, since they directly surround the photoactive layer. The above values can be used to obtain a particularly reliable and durable assembly.
In a further preferred embodiment of the invention, the optoelectronic component is characterized in that the at least one electron transport layer and the at least one hole transport layer have a length of less than 1cm 3 /(m 2 * d) And an Oxygen Transmission Rate (OTR) of less than 0.1 g/(m) 2 * d) Water Vapor Transmission Rate (WVTR). Advantageously, in particular using a hole transport layer characterized in this way, the required electrical properties can be achieved particularly reliably, while at the same time the blocking properties of the layer system required for a long lifetime are achieved. In addition, the manufacturing process is facilitated and the manufacturing cost is reduced.
In a preferred embodiment of the invention, the optoelectronic component is characterized in that at least one electron transport layer has a refractive index in the range 10 -6 cm 2 V. and 10cm 2 V. and preferably has a LUMO between 3 and 4eV, and at least one hole transport layer has a LUMO of 10 eV -6 cm 2 V. and 100 c m 2 V @, and preferably has a HOMO between 5 and 7 eV.
The mobility of the charge carriers, i.e. preferably the mobility of electrons (electron mobility) and the mobility of holes (hole mobility), preferably represents a linear scale factor between the drift velocity of the charge carriers and the electric field. This charge carrier mobility is a material property and is typically dependent on temperature. The above parameters preferably apply to room temperature of 25 c, at which the assembly is preferably used. Due to the above-mentioned charge mobility values, charge carriers are transported particularly efficiently to the recombination zone (in the case of light-emitting diodes) or to the electrode (in the case of solar cells). Thus, light emitting diodes or solar cells can be manufactured particularly efficiently. The generation of heat during operation can also be reduced, so that reliability can be improved.
LUMO (lowest unoccupied molecular orbital) denotes the lowest unoccupied orbital of a molecule of an electron transport layer in which an electron can move as a free carrier. And HOMO (highest occupied molecular orbital) represents the highest occupied orbital of the molecules of the hole transport layer in which holes can move as free carriers. The above parameters for LUMO and HOMO are optimized for the energy band of the photoactive layer, which preferably emits or absorbs electromagnetic radiation in the visible range.
By selecting suitable materials and layer thicknesses, in particular, which result in at least one electron-or hole-transport layer having the above-mentioned electrical properties or, on the other hand, in the desired blocking properties, it is possible to realize components having the desired optoelectronic properties, which at the same time also have a long lifetime. Furthermore, the performance of the assembly may be improved.
In a preferred embodiment, the optoelectronic component is characterized in that at least one electron transport layer has a doped metal oxide, preferably doped zinc oxide, wherein the doping is preferably effected with aluminum, alkali metals, alkaline earth metals, metallocenes and/or organic n-dopants, and the electron transport layer particularly preferably has aluminum zinc oxide. Surprisingly, electron transport layers made of these materials, in particular doped zinc aluminum oxide, have the characteristic of particularly good diffusion barrier properties against water and oxygen molecules and, owing to the doping, also have optimum electrical properties. It is particularly preferred that the electron transport layer is made of the above-mentioned materials and thus has a LUMO between 3 and 4eV and a LUMO between 10 eV -6 cm 2 V. and 100cm 2 V @ s. The person skilled in the art knows how to provide a material having the above-mentioned parameters without inventive effort.
In a preferred embodiment of the invention, the optoelectronic component is characterized in that the at least one hole transport layer comprises a doped metal thiocyanate (preferably doped copper thiocyanate) and/or a doped metal oxide (preferably doped zinc oxide). By means of corresponding doping, these materials can be adjusted particularly advantageously to the desired properties. In addition, they have the desired barrier properties against oxygen and water. Furthermore, these materials are very strong and therefore contribute to the manufacture of reliable assemblies. Preferably, the material is doped with a metal thiocyanate. Metal thiocyanates are particularly suitable for doping. In addition, various characteristics set by doping can be achieved using them. The metal thiocyanate is preferably selected from the group comprising sodium thiocyanate, potassium thiocyanate, silver thiocyanate, tungsten thiocyanate, vanadium thiocyanate, molybdenum thiocyanate, copper thiocyanate and/or other transition metal thiocyanates. The selection of dopants from the above-mentioned groups allows targeted adjustment of the desired electrical properties. In each case, even synergistic effects can be achieved due to the already good barrier properties of the doped base material further improved. Doping with metal oxides may also be advantageous. The metal oxides are characterized by a particularly simple and thus reliable processability. Preferably, a metal oxide to be doped selected from the group consisting of tungsten oxide, vanadium oxide, nickel oxide, copper oxide, molybdenum oxide and/or other transition metal oxides is used. They are characterized by good doping effects. Their processing requires only a few steps. However, halogen doping such as fluorine, chlorine, bromine, and iodine may be preferably used. They are characterized by their unique chemical reactivity and their high abundance in nature.
Thus, for the hole-transporting layer, preference is given to doping with metal thiocyanates, particularly preferably copper thiocyanate, or even with metal oxides, particularly preferably zinc oxide. As known to the person skilled in the art, doping in the case of optoelectronic components preferably means introducing foreign atoms (dopants) into the layer, the amount introduced being generally low compared to the support material. That is, the weight percentage of the dopant may preferably be less than 10% of the entire layer, preferably less than 1% of the entire layer. The weight percentage of dopant may also preferably be up to 40% of the total layer. With so-called p-type doping, the electron acceptor is doped, whereas for so-called n-type doping, the electron donor is doped. For the hole transport layer, a material with acceptor properties is preferably chosen, and the LUMO with the HOMO close to the carrier of a metal thiocyanate or metal oxide, preferably copper thiocyanate or zinc oxide, is preferred. For example, the organic p-type dopant may also preferably be tetrafluorotetracyanoquinodimethane (tetrafluoroottracecyanoquinodimethane) or even hexaazatriphenylenehexacyanonitriles (hexaazatriphenylenehexacyanonitriles). They have proven particularly useful. They may bring additional advantages such as higher performance and reliability and high yield.
It is particularly preferred to use copper thiocyanate or zinc oxide with the above-mentioned suitable dopants as support for the hole-transporting layer.
Surprisingly, the above-mentioned materials for the hole transport layer, in particular the use of copper thiocyanate or zinc oxide, are particularly effective in preventing the penetration of water or oxygen, while having excellent electrical properties for transporting electron holes. By doping, it is particularly preferred that the hole transport band has a thickness in the range of 10 -6 cm 2 V. and 100cm 2 V @ s, and the carrier and dopant may be selected such that the HOMO of the hole transport band is between 5eV and 7 eV. The photoactive component can therefore be operated particularly reliably and efficiently.
In a preferred embodiment of the invention, the optoelectronic component is characterized in that the total layer thickness of the at least one electron transport layer is in the range from 10 to 50nm, which is particularly robust and reliable. Therefore, it is preferable that the total layer thickness thereof is 25 to 30nm. It has been demonstrated that this is particularly maintenance-free and easy to manufacture, thereby reducing costs. The above-mentioned at least one hole transport layer has a total layer thickness of 10-40nm, which is also particularly robust and reliable. The total layer thickness is therefore preferably 10-30nm. This has also proven to be particularly maintenance-free and easy to manufacture, thus reducing costs. It is particularly preferred that the total layer thickness of the hole-transporting layer is from 15 to 25nm. This represents an improvement in electrical characteristics. The total layer thickness preferably represents the thickness of all electron-transport layers or hole-transport layers. In the case of using an electron transport layer or a hole transport layer, the thickness corresponds to the thickness of the electron transport layer or the hole transport layer. For the purposes of the present invention, thickness preferably denotes the extent of the layer along the layer structure between the electrodes and along the charge carrier transport. The above-mentioned parameters are advantageously optimized on the one hand to achieve effective protection of the photoactive layer, in particular against oxygen and water, and on the other hand to achieve a particularly thin overall structure of the photovoltaic module. Thus, a particularly durable but thin flexible assembly may be provided. Furthermore, the reliability is improved and, due to the thin, invisible layer, a particularly aesthetic effect can be achieved. These act synergistically on the aesthetic effects in the light emitting device and also contribute to an increase in the light transmission of the layers and a reduction in their scattering.
In a further preferred embodiment of the invention, the optoelectronic component is characterized in that the at least one electron injection layer or electron extraction layer and the at least one hole injection layer or hole extraction layer have a length of less than 1cm 3 /(m 2 * d) And an Oxygen Transmission Rate (OTR) of less than 1 g/(m) 2 * d) Water Vapor Transmission Rate (WVTR). A particularly effective protection of the inner elements can be ensured if these outer layers of the assembly have the above-mentioned properties. This protection already has a positive effect on the production process when the device is particularly sensitive and increases the reliability.
In this assembly, due to nano-defects in the electrodes, the flow of water and oxygen molecules into the assembly may occur. According to the invention, the transport layer for the charge carriers preferably corresponds to a diffusion barrier for these permeants. The injection or extraction layer is preferably located between the electrode and the transport layer and is preferably diffusion limited. By the above-mentioned parameters for the OTR and WVTR of the injection layer or the extraction layer, a limitation of the diffusion of, in particular, water and oxygen can be achieved. As a result, the path length of the molecules is greatly extended so that exit (e.g., through defects in the electrodes) becomes more likely than diffusion to the sensitive photoactive layer. Thus, the preferred embodiments increase the lifetime of the assembly to some extent. A particularly effective protection of the photoactive layer can be achieved due to the diffusion-limiting properties of the injection layer or the extraction layer in combination with the diffusion barrier achieved by the transport layer. The diffusion protection resulting from the combination of layers is surprisingly higher than the protection provided by the transport layer alone. As mentioned above, this effect is synergistic, i.e. the protection is significantly stronger than would be expected from the sum of the protective effects of the individual layers.
In a preferred embodiment of the invention, the optoelectronic component is characterized in that at least one electron injection layer or electron extraction layer comprises a dielectric polymer. They are characterized by a certain robustness, whereby a durable assembly can be satisfied. Their good barrier properties lead to a synergistic effect which also has a positive effect on longevity. The use of hydrophilic polymers and/or polyelectrolytes is particularly preferred. They can be particularly easy to process and thus save time, material and procedures and therefore costs. Most particularly preferably, the polymer is selected from the group consisting of poly(s)
Figure BDA0003792780690000141
A group of oxazoline, polymethacrylate, polyacrylamide, polyethylene oxide, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, and a copolymer of the group. These have proven to be particularly useful and have excellent electrical properties. The use of polyvinyl alcohol, polyethyleneimine or ethoxylated polyethyleneimine is particularly preferred, since it leads to further improvements in the components and to an increase in the performance.
The above materials are particularly suitable for ensuring the electrical function of the electron injection layer or the electron extraction layer. Thus, electrons as charge carriers can jump from the cathode into the electron transport layer (in the case of an electron injection layer) or from the electron transport layer to the cathode (in the case of an electron extraction layer) using the quantum effect of "tunneling". The above dielectric polymer preferably generates a corresponding surface dipole, thereby lowering an injection barrier of electrons. Similarly, the mobility of oxygen and water molecules in the layer is surprisingly greatly reduced or limited. Therefore, the above material is less than 1cm 3 /(m 2 * d) OTR of less than 1 g/(m) 2 * d) The preferred value of WVTR of (a) can be achieved particularly reliably.
In a preferred embodiment of the invention, the optoelectronic component is characterized in that at least one hole injection layer or hole extraction layer comprises a dielectric polymer. They have excellent barrier properties and thus improve reliability. They are preferably polymers having functional groups selected from the group comprising-CN, -SCN, -F, -Cl, -I and/or-Br, these polymers being particularly robust and maintenance-free. Therefore, the at least one hole injection layer or hole extraction layer particularly preferably comprises polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN) and/or copolymers thereof, which leads to an improvement of the assembly and an improvement of the performance.
The above materials are particularly suitable for ensuring the electrical function of the injection layer of electron holes or the extraction layer of electron holes. In particular, the above-mentioned polymers satisfy the preferred injection properties, i.e., an increase in the work function of electrons at the contact surface with the injection layer and thus efficient hole injection. In addition, the above materials have excellent barrier properties against water and oxygen. Some of the above materials have been used as food films. Surprisingly, these materials can be used to provide an injection layer or extraction layer for electron holes which simultaneously ensures a particularly energy-saving function and a particularly long lifetime of the component.
In a further preferred embodiment, the optoelectronic component is characterized in that the total layer thickness of the at least one electron injection layer or electron extraction layer is between 0.1 and 10 nm. Such layer thicknesses can be processed particularly reliably and contribute to improved electrical and optical properties. A layer thickness of between 5nm and 7nm is particularly preferred, since here, on the one hand, the desired compromise between the desired optical properties and the electrical properties is achieved, and, on the other hand, an improvement in the quality of the production method is achieved. For the at least one hole injection layer or hole extraction layer, a total layer thickness between 0.1nm and 10nm is preferred. The advantages of being suitable for an electron injection layer or an electron extraction layer apply here as well. The same applies to particularly preferred layer thicknesses between 5nm and 7 nm. The total layer thickness preferably quantifies the total extent of each electron injecting layer or electron extracting layer or each hole injecting layer or hole extracting layer. In the case of layers, the total layer thickness is preferably equal to the thickness of the layer, otherwise equal to the sum of the thicknesses of the layers. The inventors have found that the above-mentioned layer thicknesses surprisingly have excellent barrier properties against water and oxygen and an effective "tunneling effect", thereby achieving an electrical function.
In a further preferred embodiment of the invention, the optoelectronic component is characterized in that it has at least two electron-injecting or electron-extracting layers, at least two electron-transporting layers, at least two hole-transporting layers and at least two hole-injecting or hole-extracting layers, wherein the electron-injecting or electron-extracting layers and the electron-transporting layers and the hole-injecting or hole-extracting layers and the hole-transporting layers are arranged in an alternating arrangement. For the purposes of the present invention, alternating preferably means that the injection layers or extraction layers preferably alternate with the transport layers. For example, a preferred layer structure for two electron transport layers and two electron injection layers is as follows: a first injection layer adjoins the cathode, followed by a first transport layer, a second injection layer, and a second transport layer, the second transport layer adjoining the photoactive layer. By preferably using a plurality of injection layers and transport layers, a particularly effective protection against penetration of water and oxygen can be achieved. By alternating the arrangement, even a small thickness of the individual layers results in a surprising improvement of the barrier properties of the layers. This synergistic effect is greater than that exhibited by the sum of the barrier properties of the individual layers, particularly in the case of an alternating arrangement of layers.
In a further preferred embodiment of the invention, the photovoltaic module is characterized in that the anode comprises a metal, a metal oxide, a metal thiocyanate, a metal nanowire and/or a mixture of these materials. The advantage of these materials is that they are particularly easy to process. Preferably, the metal nanowires are silver nanowires and/or metal oxide nanowires. They have particularly excellent optical and electrical properties, thus providing improvements and enhancements in component performance. The metal oxide is preferably a transition metal oxide or a metal oxide doped with a metal and/or a halogen. They are characterized by a particularly high work function and increase the effectiveness of the assembly. Among the above materials, indium zinc oxide and/or zinc fluoride oxide are particularly preferable. These materials are particularly robust and therefore have improved reliability. The metal thiocyanates are preferably transition metal thiocyanates, since they are easy to process and therefore reduce costs. Tungsten thiocyanate and/or copper thiocyanate are particularly preferred. These materials have proven to be particularly maintenance-free and have an extended service life. Furthermore, they can be in good electrical contact.
All the above-mentioned materials perform particularly well the function of an anode, act as a donor of electron holes, have a high work function and a regional conductivity for the electron holes. In addition, the anode material can particularly preferably be selected such that it is transparent to visible light, since the anode is preferably used for discharging the electromagnetically generated radiation (in the case of light-emitting diodes). In addition, the material preferably has barrier properties to water or oxygen such that all OTR or WVTR of the electrode, injection layer or combination of extraction layer and transport layer are preferably less than 0.01cm 3 /(m 2 * d) Or 0.01 g/(m) 2 *d)。
However, all OTRs or WVTRs of the combination of electrode, injection layer or extraction layer and transport layer may also preferably be less than 0.1cm 3 /(m 2 * d) Or 0.1 g/(m) 2 * d) In that respect The desired OTR or WVTR characteristics may be influenced correspondingly by the appropriate layer thickness of the anode material and the material and thickness of the other layers.
Particularly preferably, the anode is made of Indium Tin Oxide (ITO), with a particularly preferred layer thickness of about 150nm. For the purposes of the present invention, details such as about, about or synonymous terms are preferably to be understood as a tolerance of ± 10%, particularly preferably ± 5%. In a further particularly preferred variant, bao Yinceng (preferably with a layer thickness of about 2 nm) is also applied to the ITO. This further improves performance. In a further preferred variant, the anode consists of an ITO layer of about 150nm, a silver layer of about 2nm and a further layer of tungsten oxide (WO with a layer thickness of preferably about 2 nm) 3 ) And (4) forming. Advantageously, the application of these metal layers allows for a good supply of electron holes. Furthermore, the material is highly transparent at layer thicknesses of 1nm to 5nm. Because tungsten oxide has a higher work function than silver, the preferred light emitting diodes can operate at particularly low operating voltages. Furthermore, in particular for the above embodiments, it may also be preferred that the ITO is replaced by fluorine-doped tin oxide (FTO) or chlorine-doped tin oxide (CTO) or chlorine-doped zinc oxide (CZO) or fluorine-doped zinc oxide (FZO), or by metal nanowires embedded in a matrix of FTO, CTO, CZO or FZO, the metal nanowires preferably being silver nanowires. Due to their preferred lightThe above materials contribute to the performance of the assembly. Likewise, the increased brightness and reduced scattering resulting therefrom achieve a particular aesthetic effect.
In a further preferred embodiment, the photovoltaic module is characterized in that the layer thickness of the anode is between 50 and 500 nm. Thus, a compact and flexible construction method of the optoelectronic component with the desired optical properties can be achieved. Likewise, the desired OTR or WVTR characteristics of the entire layer system can be achieved. Furthermore, the electrical contacting of the anode is facilitated by the layer thickness and provides the required mechanical stability of the anode.
In a preferred embodiment, the photovoltaic module is characterized in that the cathode comprises a metal, a metal oxide, a metal thiocyanate, a metal nanowire and/or a mixture of these materials. These materials are particularly robust and maintenance free. The metal is preferably selected from the group comprising aluminum, copper, gallium, indium, tin, cobalt, nickel, which have good processability and thus simplify manufacturing. The metal nanowires are preferably silver nanowires and/or metal oxide nanowires, which improve the performance of the assembly. The cathode particularly preferably comprises metal oxides doped with metals which improve the quality of the component. Particularly preferably, the cathode comprises zinc oxide doped with aluminum, which allows for improved electrical properties.
These materials enable the work function of the cathode to be optimized, in particular in the case of light-emitting diodes, for the optimal supply of electrons. Thus, a particularly low sheet resistance can be achieved in order to promote the most uniform possible injection of electrons across the cathode surface.
Particularly preferably, the cathode consists of a metal layer, preferably silver, which is preferably printed. In manufacturing this means saving time, material and process steps and thus costs. Likewise, silver has desirable optical (reflective) properties in the visible wavelength range. Alternatively, however, vapor deposition of metals may be preferred. Vapor deposition of metals improves reliability during the manufacturing process. In addition to silver, other metals may preferably be used, such as aluminum, copper, gallium indium tin alloy or alloys. These materials have good processability. The thickness of the cathode of these materials is preferably between 50nm and 500 nm. Cathodes of this thickness can be produced particularly reliably. A layer thickness of the cathode of about 150nm is particularly preferred. Cathodes of this thickness are particularly effective.
In a further preferred variant, the cathode consists of a layer made of printed metal nanowires. Such a cathode can be manufactured particularly reliably and cost-effectively. Preferably, they are silver nanowires. They contribute to improved performance, especially due to good optical and electrical properties. Alternatively, copper, cobalt or nickel nanowires may be preferably used. They can be processed particularly well and increase the reliability. The metal nanowire layer preferably also has a thickness of between 30nm and 500nm, which can be produced particularly reliably, is very robust and can be electrically contacted particularly easily. Layer thicknesses of about 150nm are particularly preferred. They can be produced in a particularly error-free manner. The metal nanowires may preferably be embedded in a metal oxide matrix made of aluminum-doped zinc oxide. Thus, particularly advantageous electrical characteristics can be achieved. The cathode may particularly preferably be transparent. A particularly transparent light emitting diode may be provided together with a preferably transparent anode. Due to the double-sided radiation properties, a particularly aesthetic and surprising effect is achieved which can be used, for example, in print advertising.
Furthermore, the required OTR or WVTR properties of the layer system comprising the cathode can be achieved by the above-mentioned materials and thicknesses of the cathode.
In addition, it may be preferable to adhere a metal film to the metal nanowire of the cathode. Thus, increased reflection and increased light emission may be obtained from the transparent anode. The metal film may preferably be a commercial aluminum film having a thickness of about 50 μm. Thus, the cost can be reduced. However, the metal film may also have a thickness of 10 μm to 100 μm. An advantage of this embodiment is that the desired properties regarding the robustness, the degree of reflection and the flexibility of the assembly can be flexibly selected. In addition, the preferred metal films used may also be made of copper or other metals. Thus, the light output can be increased and adjusted.
In a further preferred embodiment, the photovoltaic module is characterized in that the layer thickness of the cathode is between 50 and 500 nm. Thus, another approach is provided that has a broad impact on electrical and optical properties. Preferably, the cathode should have a layer thickness between 100nm and 200 nm. Such cathodes have proven to be particularly robust.
In a further preferred embodiment of the invention, the optoelectronic component is characterized in that the photoactive layer is an emission layer, the emission spectrum of which preferably lies in the wavelength range between 400nm and 700 nm. The light generating layer is preferably composed of semiconducting organic polymers or molecules that generate light in the visible range, preferably between 400nm and 700nm, when electrically stimulated (i.e. a voltage is applied to the electrodes). Preferably, the thickness of the emission layer is 15nm to 100nm. Thus, an increase of the performance of the light generation layer with respect to its efficiency and overall optical properties is achieved. Particularly preferably, the thickness of the emission layer is 40-60nm. Such an emitter layer is very reliable and maintenance free. In a preferred variant, the light generating layer consists of 95 wt% of a polymer that generates light in the visible spectrum upon electrical stimulation and 5 wt% of a polymer having a higher bandgap than the light generating polymer. In this preferred variant, monochromatic light can be produced. In a further preferred embodiment, the emissive layer consists entirely of a polymer that produces light in the visible spectrum upon electrical stimulation. Such an emitter layer is particularly robust. In addition, the emissive layer may preferably have various dopants to increase conductivity and thus efficiency (e.g., aluminum quinolate, tetracyanoquinodimethane, molybdenum oxide nanoparticles, metallocenes), or to modify the emission spectrum and electron-photon efficiency (e.g., quinoline iridium complex). However, for the purposes of the present invention, completely different emissive layers may be advantageously used. The emissive layers react most readily with water or oxygen, so their efficiency is largely dependent on exposure to these molecules. By providing an optical assembly that effectively protects photoactive layers (e.g., emissive layers) from water and oxygen permeation, a wide variety of layers can be used and tailored for respective applications. Preferred embodiments that emit in the visible spectrum are particularly suitable for commercial applications.
In a further preferred embodiment of the invention, the optoelectronic component is characterized in that the photoactive layer is an absorption layer, the absorption spectrum of which preferably lies in the range between 300nm and 1500 nm. Preferably, a polymer layer which absorbs electron radiation, preferably solar radiation, and generates free electron-hole pairs can be used as the absorbing layer. By the preferable range, the solar cell can be widely used. Advantageously, many materials known in the art may be used for the absorbent layer. In particular, the exclusion criteria associated with sensitivity to water or oxygen relate to a compromise in lifetime, since the barrier properties of the further electrical layer effectively protect the photoactive layer.
In a preferred embodiment, the invention also relates to a method for producing a photovoltaic module according to the invention or preferred embodiments thereof, wherein the method is characterized in that the electron injection layer, the electron transport layer, the photoactive layer, the hole transport layer and/or the hole injection layer are applied by wet-chemical methods and/or thermal evaporation methods. These methods represent an improvement in relation to the prior art and are particularly reliable. It is particularly preferred that these layers are applied by screen printing, spin coating, offset printing and/or gravure printing. These methods can save time, materials, procedures and costs. It is particularly preferred to apply these layers by an ink-jet printing process. The method is particularly robust and efficient and results in an improved quality compared to conventional methods. The cathode and the anode can particularly preferably be applied by spraying. The method improves reliability and reduces manufacturing cost.
Therefore, it is particularly preferred that the transport layer and the injection or extraction layer can be stably treated in air. The materials described above and the method described here for applying the layers are particularly suitable for this purpose. "stable treatment in air" means in particular that all steps required for producing the component, in particular the application of the layers, can be carried out in the ambient room air without restrictions and without special precautions. Thus, cost and time may be saved and efficiency may be improved during manufacturing.
Preferably, wet-chemical processes are understood to mean manufacturing processes in which the materials (e.g. polymers) for the individual layers are present in solutions and are coated using these solutions. Suitable solvents are known to those skilled in the art as carriers for the components. Thermal vapor deposition is understood to mean the preferred vacuum-based coating method, in which the material for the layer is heated to the boiling point and is thus vapor-deposited onto the corresponding substrate.
By the above-described method, a particularly uniform pure layer with a well-defined expansion can be applied. The inkjet printing method for electrical and photoactive layers and the spray coating method for electrodes are also characterized by particularly low manufacturing costs and broad applicability to various substrates. Most importantly, this process can be achieved without any special effort, in particular without the use of special vacuum or plenum chambers, due to the processability of the electroactive layer in air.
Hereinafter, the present invention will be described in more detail using examples, but is not limited to these embodiments.
Drawings
Fig. 1 is a schematic view of a layer structure of a conventional photovoltaic module encapsulated by a barrier film.
Fig. 2 is a schematic enlarged view of the layer structure of a barrier film for a conventional optical member.
Fig. 3 is a schematic diagram of a preferred embodiment of an opto-electronic assembly according to the invention.
Detailed Description
Fig. 1 and 2 show a schematic structure of a conventional photovoltaic module 1, the photovoltaic module 1 being encapsulated by a barrier film 17. The layer structure of the component 1 shown is that of a light-emitting diode and is constructed as follows. Upon application of a voltage to the cathode 3 and the anode 5, the cathode 3 serves to supply electrons, and the anode 5 supplies holes. The symbols + and-each preferably show the voltage direction. The properties of the electron injection layer 7 and the hole injection layer 9 preferably allow for an efficient quantum mechanical tunneling of charge carriers to the transport layer. The electron transport layer 11 and the hole transport layer 13 are characterized by a high mobility of the charge carriers and ensure a targeted transport to the emission layer 15. In the emission layer 15, the charge carriers recombine to generate excitons and emit visible light 2. The penetration of water or oxygen into the emissive layer can significantly reduce the efficiency coefficient and thus the lifetime. For this reason, in the prior art, the photovoltaic module 1 is encapsulated by a barrier film 17, the barrier film 17 being used to prevent the penetration of water and oxygen. For this purpose, it is customary in the prior art to choose an alternating layer structure in which the diffusion-limiting layers 19 alternate with diffusion-blocking layers or barrier layers 21. The diffusion barrier or barrier layer 21 should prevent molecular diffusion. However, it is also possible for molecules to diffuse through small defects. Due to the diffusion limiting layer 19 the path length of the molecules is extended so that they re-emerge preferably through defects in the diffusion barrier layer or barrier layer 21. Further, in the prior art, the barrier film includes a carrier substrate 23.
Fig. 3 shows a schematic view of a preferred embodiment of the opto-electronic assembly according to the invention. The layer structure of the optoelectronic component 1 shown is that of a light-emitting diode. The basic function of the layers in the layer structure is the same as that of the conventional photovoltaic module according to fig. 1 or 2. Upon application of a voltage to cathode 25 and anode 27, cathode 25 is used to provide electrons and anode 27 provides holes. The symbols + and-each preferably show the voltage direction. In addition, however, cathode 25 and anode 27 have barrier properties to water and oxygen molecules, thus providing a diffusion barrier for the permeate.
The electrical properties of the electron injection layer 29 and the hole injection layer 31 preferably allow for an effective quantum mechanical tunneling of charge carriers to the transport layer. Meanwhile, the materials of the electron injection layer 29 and the hole injection layer 31 are selected so that they have a diffusion limiting effect on water molecules and oxygen molecules, thereby extending the diffusion length of molecules in each layer.
The electron transport layer 33 and the hole transport layer 35 are characterized by a high mobility of the charge carriers and ensure a targeted transport to the emission layer 15. In the emission layer 15, the charge carriers recombine to generate excitons and emit visible light 2.
However, in contrast to the prior art, the electron transport layer 33 and the hole transport layer 35 provide diffusion barriers to water and oxygen. The layer structure according to the invention thus facilitates an alternating layer structure of diffusion limiting layers and diffusion barrier layers in the same way as barrier films of the prior art. However, it has been found in accordance with the present invention that the electroactive layers (electron injection layer 29, hole injection layer 31, electron transport layer 33, and hole transport layer 35) and the electrodes (cathode 25 and anode 27) themselves can serve as a diffusion limiting layer and a diffusion barrier layer. Thus, it is possible to provideThe electron transport layer 33, the hole transport layer 35, the cathode 25 and the anode 27 act as diffusion barriers, which should reduce the diffusion of water or oxygen molecules. The electron injection layer 29 and the hole injection layer 31 function as diffusion limiting layers, which extend the path length of molecules, and thus can compensate for defects of the diffusion barrier layer. In a preferred embodiment, the OTR of the layer combination of the cathode 25, the diffusion limited electron injection layer 29 and the electron transport layer as diffusion barrier layer 33 is less than 0.1cm 3 /(m 2 * d) Preferably less than 0.01cm 3 /(m 2 * d) And has a WVTR of less than 0.1 g/(m) 2 * d) Preferably less than 0.01 g/(m) 2 * d) In that respect Likewise, the OTR of the layer combination of anode 27, diffusion limited hole injection layer 31 and hole transport layer as diffusion barrier layer 35 is less than 0.1cm 3 /(m 2 * d) Preferably less than 0.01cm 3 /(m 2 * d) And has a WVTR of less than 0.1 g/(m) 2 * d) Preferably less than 0.01 g/(m) 2 *d)。
These parameters prevent water and oxygen molecules from penetrating into the emissive layer 15 and significantly extend the lifetime. Advantageously, this does not require complex and expensive barrier films that increase the overall thickness of the photovoltaic assembly 1.
It should be noted that various alternatives to the embodiments of the invention described may be employed in practicing the invention and obtaining a solution in accordance with the invention. The optoelectronic component according to the invention and its production in the method are not limited in their embodiment to the preferred embodiments described above. On the contrary, various design variations from the shown solution are conceivable. The aim in the appended claims is to determine the scope of the invention. The scope of protection of the claims is intended to cover the photovoltaic module according to the invention and its manufacturing method and equivalent embodiments.
List of reference numerals
1. Optoelectronic component
2. Light (es)
3. Cathode electrode
5. Anode
7. Electron injection layer
9. Hole injection layer
11. Electron transport layer
13. Hole transport layer
15. Emissive layer
17. Barrier film
19. Diffusion limiting layer
21. Diffusion barrier layer
23. Carrier substrate
25. Cathode as diffusion barrier layer
27. Anode as diffusion barrier
29. Diffusion limited electron injection layer
31. Diffusion limited hole injection layer
33. Electron transport layer as diffusion barrier
35. Hole transport layer as diffusion barrier

Claims (19)

1. Optoelectronic component (1) having a cathode (25) and an anode (27) and a layer system between the cathode (25) and the anode (27), comprising:
-at least one electron injection layer (29) or electron extraction layer adjacent to the cathode,
-at least one electron transport layer (33),
-at least one photoactive layer,
-at least one hole transport layer (35),
-at least one hole injection layer (31) or hole extraction layer adjacent to the anode,
it is characterized in that the preparation method is characterized in that,
the at least one electron injection layer (29) or electron extraction layer and the at least one hole injection layer (31) or hole extraction layer are diffusion-limited to water and/or oxygen, and
the at least one electron transport layer (33) and the at least one hole transport layer (35) act as diffusion barriers for water and/or oxygen.
2. Optoelectronic component (1) according to the preceding claim,
it is characterized in that the preparation method is characterized in that,
a cathode (25), the at least one electron injection layer (29) or electron extraction layer andthe layer combination of the at least one electron transport layer (33) has a value of less than 0.1 g/(m) 2 * d) And a Water Vapor Transmission Rate (WVTR) of less than 0.1cm 3 /(m 2 * d) Oxygen Transmission Rate (OTR), and/or
The layer combination of the anode (27), the at least one hole injection layer (31) or hole extraction layer and the at least one electron transport layer (35) has a value of less than 0.1 g/(m) 2 * d) And a Water Vapor Transmission Rate (WVTR) of less than 0.1cm 3 /(m 2 * d) Oxygen Transmission Rate (OTR).
3. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the at least one electron transport layer (33) and the at least one hole transport layer (35) have a thickness of less than 1cm 3 /(m 2 * d) And an Oxygen Transmission Rate (OTR) of less than 0.1 g/(m) 2 * d) Water Vapor Transmission Rate (WVTR).
4. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the at least one electron transport layer (33) has a thickness in the range of 10 -6 cm 2 V. and 100cm 2 V. and preferably has a LUMO between 3 and 4eV, and
the at least one hole transport layer (35) has a thickness of 10 -6 cm 2 V. and 100cm 2 V x s, and preferably has a HOMO between 5 and 7 eV.
5. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the at least one electron transport layer (33) has a doped metal oxide, preferably doped zinc oxide, wherein the doping is preferably carried out with aluminum, alkali metals, alkaline earth metals, metallocenes and/or organic n-dopants, and the electron transport layer (33) particularly preferably has aluminum zinc oxide.
6. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the at least one hole transport layer (35) has a doped metal thiocyanate, preferably doped copper thiocyanate, and/or a doped metal oxide, preferably doped zinc oxide,
preferably doped with a metal thiocyanate, preferably selected from the group comprising sodium thiocyanate, potassium thiocyanate, silver thiocyanate, tungsten thiocyanate, vanadium thiocyanate, molybdenum thiocyanate, copper thiocyanate and/or other transition metal thiocyanates, and/or
Preferably doped with a metal oxide, preferably selected from the group comprising tungsten oxide, vanadium oxide, nickel oxide, copper oxide, molybdenum oxide and/or other transition metal oxides, and/or
Halogen doping is preferred, and fluorine is particularly preferred.
7. Optoelectronic assembly according to any one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the total layer thickness of the at least one electron transport layer (33) is 10 to 50nm, preferably 25 to 30nm, and the total layer thickness of the at least one hole transport layer (35) is 10 to 40nm, preferably 10 to 30nm, particularly preferably 15 to 25nm.
8. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the at least one electron injection layer (29) or electron extraction layer and the at least one hole injection layer (31) or hole extraction layer have a thickness of less than 1cm 3 /(m 2 * d) And an Oxygen Transmission Rate (OTR) of less than 1 g/(m) 2 * d) Water Vapor Transmission Rate (WVTR).
9. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the at least one electron injection layer (29) or electron extraction layer comprises a dielectric polymer, preferably a hydrophilic polymer and/or a polyelectrolyte, particularly preferably a polymer selected from the group consisting of poly (meth) acrylates
Figure FDA0003792780680000031
Polymers selected from the group of oxazolines, polymethacrylates, polyacrylamides, polyethylene oxides, polyacrylic acids, polyacrylates, polyvinylpyrrolidones and copolymers thereof, most particularly preferably including polyvinyl alcohol, polyethyleneimine or ethoxylated polyethyleneimine.
10. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the at least one hole injection layer (31) or hole extraction layer comprises a dielectric polymer, preferably a polymer having functional groups selected from the group comprising-CN, -SCN, -F, -Cl, -I and/or-Br, particularly preferably polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC) or Polyacrylonitrile (PAN) and copolymers thereof.
11. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the total layer thickness of the at least one electron injection layer (29) or electron extraction layer is between 0.1nm and 10nm, preferably between 5nm and 7nm,
the total layer thickness of the at least one hole injection layer or hole extraction layer is between 0.1nm and 10nm, preferably between 5nm and 7 nm.
12. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the component (1) has at least two electron injection layers (29) or electron extraction layers, at least two electron transport layers (33), at least two hole transport layers (35) and at least two hole injection layers (31) or hole extraction layers,
wherein the electron injection layer (29) or electron extraction layer and the electron transport layer (33) and the hole injection layer (31) or hole extraction layer and the hole transport layer (35) are arranged in an alternating arrangement.
13. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the anode (27) comprises a metal, a metal oxide, a metal thiocyanate, a metal nanowire, a halogen and/or a mixture of these metals, wherein preferably the metal nanowire is a silver nanowire and/or a metal oxide nanowire, preferably a transition metal oxide, a metal-doped metal oxide or a halogen-doped metal oxide, particularly preferably indium tin oxide, preferably a halogen-doped metal oxide, preferably zinc fluoride oxide, and the metal thiocyanate is preferably a transition metal thiocyanate, particularly preferably tungsten thiocyanate and/or copper thiocyanate.
14. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the layer thickness of the anode (27) is between 50nm and 500 nm.
15. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the cathode (25) comprises a metal, preferably selected from the group comprising aluminum, copper, gallium, indium, tin, cobalt, nickel, metal nanowires, preferably silver nanowires and/or metal oxide nanowires, a metal oxide, particularly preferably doped with a metal, particularly preferably doped with aluminum zinc oxide, and/or mixtures of these materials.
16. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the layer thickness of the cathode (25) is between 50nm and 500nm, preferably between 100nm and 200 nm.
17. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the photoactive layer is an emission layer (15) having an emission spectrum preferably in the wavelength range between 400nm and 700 nm.
18. Optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the photoactive layer is an absorption layer, the absorption spectrum of which is preferably in the range between 300nm and 1500 nm.
19. A method for producing an optoelectronic component (1) according to one of the preceding claims,
it is characterized in that the preparation method is characterized in that,
the electron injection layer (29), the electron transport layer (33), the photoactive layer, the hole transport layer (35) and/or the hole injection layer (31) are applied using a wet-chemical method and/or a thermal evaporation method, wherein it is particularly preferred that these layers are applied by screen printing, spin coating, offset printing and/or gravure printing, and it is particularly preferred that they are applied by an inkjet printing method, and the cathode and the anode are particularly preferably applied using a spray coating method.
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